The construction of devices and materials through molecular self-assembly and self-organization processes is of considerable interest.[1-7] This invention relates to methods for controlling the self-organization of organic compounds, particularly into a lyotropic (solvent- and concentration-dependent) liquid-crystalline phase, in order to prepare micro-patterned organic solids in which molecular orientation and anisotropic (direction-dependent) properties are controlled or selected.
Patterned anisotropic solids have significant commercial applications, particularly in the fields of microelectronics and optics. Patterned inorganic semiconducting materials are generally useful in the field of microelectronics e.g. as transistors and electronic circuits. Patterned organic semiconducting materials are expected to be useful in similar applications, where the anisotropic orientation of the molecules in these organic materials can enhance the conducting properties of these materials e.g. anisotropic conducting properties. In the field of optics, patterned anisotropic solids have application as holographic films, as viewing angle-dependent optical materials, for use in stereoscopic displays, for use as polarizers, diffraction gratings, circular polarizers on retarders, waveguides, and as photonic materials.[8, 9]
A wide range of methods is available for the micro- and nano-patterning of isotropic (direction-independent) materials including photolithography,[10] soft lithography,[11, 12] e-beam lithography, and scanning probe techniques[13, 14] However, currently available methods for micro-patterning of anisotropic organic materials are limited to methods that employ either uniaxially stretched polymer films[15] or a photoalignment technique.[9] The method of the present invention generates micro-patterns and nano-patterns of anisotropic organic materials by exploiting the self-organization of organic and organometallic compounds, particularly chromonic liquid crystals on templates.
U.S. Pat. Nos. 5,405,962; 5,650,513; 5,808,073; 5,986,099; and 6,124,458 and WO 96/22332 relate to the synthesis of quaterrylenetetracarbimides and derivatives thereof. Each of these patent documents is incorporated by reference herein in its entirety to the extent that it is not inconsistent with the disclosure herein for descriptions of methods of synthesis, sources of starting materials and methods of making derivatives of quaterrylenes, as well as for structures of various art-known quaterrylene derivatives. These patents also provide descriptions of applications of certain quaterrylene derivatives.
U.S. Pat. No. 6,136,976 relates to syntheses of certain perylene-3,-4-dicarboxylic acid imides and certain applications of the compounds disclosed. U.S. Pat. No. 6,166,210 relates to certain perylene imide monocarboxylic acids and certain applications of the compounds disclosed. U.S. Pat. No. 5,948,910 relates to certain water-soluble perylene dyestuffs. U.S. Pat. No. 5,508,137 relates to certain perylene amidine imide dyes. U.S. Pat. No. 5,466,807 relates to certain perylene compounds containing sulfonic acid groups in particular, compounds based on perylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimides which are substituted by alkylene- or arylenesulfonic acid groups on one or both imide nitrogen atoms, or on corresponding tetracarboxylic acid diimides, or on a halogenation product thereof which are reported to be useful as pigments and fluorescent dyestuffs as well as polymer-soluble dyestuffs. U.S. Pat. No. 4,719,236 relates to certain perylene derivatives particularly ether derivatives. U.S. Pat. No. 6,784,301 relates to certain perylene derivatives which are reported to be crystallization modifiers. Each of these patent documents is incorporated by reference herein in its entirety to the extent that it is not inconsistent with the disclosure herein for descriptions of methods of synthesis, sources of starting materials and methods of making perylene derivatives, as well as for structures of various art-known perylene derivatives. These patents also provide descriptions of certain applications of perylene derivatives.
U.S. published patent application 200424151A1 (published Feb. 5, 2004) relates to the use of functionalized perylene-3,4,9,10-tetracarboxylic acid diimides as initiator and/or co-reactant for polymerization reactions, to polymers prepared using the perylene-3,4,9,10-tetracarboxylic acid diimide compounds, to the use of the colored and/or fluorescent polymers, and to certain functionalized perylenetetracarboxylic acid diimides. This reference is incorporated herein in particular for descriptions of method of synthesis, sources of starting materials and methods of making derivatives as well as for structures of various art-known perylene derivatives.
U.S. Pat. No. 6,049,428 and references cited therein relate to dichroic light polarizers made employing dichroic dyes of a number of specific formulas. Dichroic dyes of formulas I-XXXIV therein can be employed as discussed hereinbelow in the methods of this invention to make anisotropic solids. This patent is incorporated by reference herein at least in part for its description of certain dichroic dyes. U.S. Pat. No. 6,174,394 relates to a method of making polarizers employing a polarizing coating formed from dyes having a stable liquid crystalline phase. This patent is incorporated by reference herein at least in part for its description of a method of making polarizers.
U.S. Pat. No. 6,149,857 relates to methods of making films and coatings having anisotropic conductive pathways there between.
U.S. Pat. Nos. 6,411,354, and 6,570,632 relate to alignment of lyotrophic liquid crystals. U.S. published application 2003 0154909 A1 and corresponding published PCT application WO 02/063660 relate to methods for obtaining anisotropic crystalline films and devices employed in the method. These patent documents are incorporated by reference herein at least in part for descriptions of alignment of lyotrophic liquid crystals and methods for obtaining anisotropic films which can also be employed with compounds of this invention.
Each of the following publications of the inventors hereof is incorporated by reference herein in its entirety I. K. Iverson and S-W. Tam-Chang (1999) J. Am. Chem. Soc. “Cascade of Molecular Order by Sequential Self-Organization, Induced Orientation, and Order Transfer Processes” 121:5801-5802; I. K. Iverson, S. M. Casey, W. Seo, S-W Tam-Chang (2002) “Controlling Molecular Orientation in Solid Films via Self-Organization in the Liquid Crystalline Phase” Langmuir 18:3510-3516; I. K. Iverson “Aggregation and Self-Organization of Perylene-diimide Dye Analogs into Liquid Crystalline Phases and Subsequent Order Transfer to the Solid Phase” Doctoral Dissertation, University of Nevada Reno, dated May 2002; S-W. Tam-Chang, W. Seo, I. K. Iverson, and S. M. Casey (2003) “Ionic Quaterrylenebis(dicaroxyimide): A Novel Mesogen and Long-Wavelength Polarizing Material” Angew. Chem. Int. Ed. 42(8):897-900. (Feb. 21, 2003); and T. D. Carson, W. Seo, S-W, Tam-Chang, and S. M. Casey “Novel Polarized Photoluminescent Films Derived from Sequential Self-Organization, Induced-Orientation, and Order-Transfer Processes” (2003) Chem. Mater. 15, 2292-2294.
Long-wavelength absorbing and/or emitting compounds are useful as fluorescent dyes and probes for biological studies and for sensors. These compounds also have applications in areas such as optical recording, thermally-written displays, laser printers, laser filters, infrared photography, fiber-optic communications, and optical applications in conjunction with commercially available GaAlAs lasers that emit around 780 nm. (Law, K. Y. Chem. Rev. 1993, 93, 449-486; Emmelius, M.; Pawlowski, G.; Vollmann, H. W. Angew. Chem. Int. Ed. Eng. 1989, 28, 1445-1600.) Near-Infrared (NIR) polarizers have applications as optical isolators that are used in conjunction with semiconductor lasers and fiber optics (U.S. Pat. No. 5,278,853).
There are examples of non-ionic quaterrylenebis(dicarboximide)s that absorb and emit at long wavelengths (red and near-infrared), but these compounds are soluble only in concentrated sulfuric acid (strongly oxidizing and corrosive) and chlorinated organic solvents (up to only about 10−2 M). Their limited solubility limits their processibility. (Quante, H.; Mullen, K. Angew. Chem. Int. Ed. Engl. (1995), 34, 1323-1325; Geerts, Y.; Quante, H.; Platz, H.; Mahrt, R.; Hopmeier, M.; Bohm, A.; Mullen, K. J. Mater. Chem. 1998, 8, 2357-2369.)
Thermotropic liquid-crystalline perylenebis(dicarboximide)s and lyotropic ionic perylenebis(dicarboximide)s have been previously reported. (Law, K. Y. Chem. Rev. (1993) 93, 449-486; Würthner, F.; Sautter, A.; Schmid, D.; Weber, P. J. A. Chem. Eur. J. (2001) 7, 894-902; Würthner, F.; Sautter, A. Chem. Commun. 2000, 445446; Gregg, A. B.; Cormier, R. A. J. Am. Chem. Soc. (2001), 123, 7959-7960; Schenning, A. P. H. J.; Herrikhuyzen, J. V.; Jonkheijm, P.; Chen, Z.; Würthner, F.; Meijer, E. W. J. Am. Chem. Soc. (2002), 124, 10252-10253; Daffy, L. M.; de Silva, A. P.; Gunaratne, H. Q. N.; Huber, C.; Lynch, P. L. M.; Werner, T.; Wolfbeis, O. S. Chem.-Eur. J. (1998) 4, 1810-1815; Langhals, H. Heterocycles (1995) 40, 447-500; Holtrup, F. O.; Müller, G. R. J.; Quante, H.; De Feyter, S.; De Schryver, F. C.; Müllen, K. Chem.-Eur. J. (1997), 3, 219-225; O'Neil, M. P.; Niemczyk, M. P.; Svec, W. A.; Gosztola, D.; Gaines, G. L.; Wasielewski, M. R. Science (1992) 257, 63-65; Gregg, B. A. J. Phys. Chem. (1996) 100, 852-859; Schmidt-Mende, L.; Fechtenkötter, A.; Müllen, K.; Moons, E.; Friend, R. H.; MacKenzie, J. D. Science (2001) 293, 1119-1122; Langhals, H.; Ismael, R.; Yürük, O. Tetrahedron (2000) 56, 5435-5441; Würthner, F.; Thalacker, C.; Diele, S.; Tschierske, C. Chem. Eur. J. (2001) 7, 2245-2253; Cormier, R. A.; Gregg, B. A. J. Phys. Chem. B. (1997)101, 11004-11006; Cormier, R. A.; Gregg, B. A. Chem. Mater. (1998) 10, 1309-1319; Liu, Z.-R.; Rill, R. L. Anal. Biochem. (1996) 236, 139-145; Tuntiwechapikul, W.; Lee, J. T.; Salazar, M. J. Am. Chem. Soc. (2001) 123, 5606-5607.)
Dichroic compounds that are commercially available as carboxylate dyes or sulfonated dyes or synthesized by the sulfonation of azo or polycyclic compounds can be used for the fabrication of dichroic thin film (absorption) polarizers by the mechanical shearing of lyotropic liquid-crystalline phases of these sulfonated dyes in the presence of surfactants and additives. (Gvon, Khan Ir.; Bobrov, Yuri A.; Bykov, Victor A.; Ignatov, Leonid Y.; Ivanova, Tatianna D.; Popov, Sergei I.; Shishkina, Elena Y.; Vorozhtsov, Georgiy N. “Thermostable and Lighffast Dichroic Light Polarizers” PCT/US94/05493. International publication number WO 94/28073; Khan, Ir Gvon; Bobrov, Yuri A.; Ignatov, Leonid Y.; Shishkina, Elena Y.; Lazarev, Pavel I.; Kurbatov, Alexey V. “Dichroic Light Polarizers” PCT/US95/14413. U.S. Pat. No. 6,049,428; Bobrov, Y.-A.; Casey, S. M.; Ignatov, L. Y.; Lazarev, P.; Phillips, D.; Tam-Chang, S.-W. “Novel Dichroic Polarizing Materials and Approaches to Large Area Processing” in Flat Panel Display Materials-1998, edited by Parsons, G.; Fahlen, T. S.; Morozumi, S.; Seager, C.; Tsai, C-C. (Mater. Res. Soc. Proc., Warrendale, Pa., 1998), pp. 225-228.)
Major drawbacks of this technique for making polarizers include the required use of large quantities of highly corrosive solvents and reagents for the synthesis of sulfonate dyes making them difficult to use and expensive to dispose of; the sulfonated dyes used are often not well defined in structure; the mixtures of products is hard or impossible to separate and purify and as a result, the properties of lyotropic liquid crystals of these dyes and the optical performance of the resultant thin dichroic polarizers are hard to control and reproduce; the carboxylate dyes are not stable to storage and insoluble particles may be generated which lead to thin films with poor optical properties. Additionally, the need for surfactants and additives further complicates the optimization of the optical performance of the polarizing materials.
It is believed that this method for preparing dichroic thin film polarizers (based on the mechanical shearing of lyotropic liquid crystals) has only been used for the preparation of dichroic thin film polarizers. It has not been used, for example, for the fabrication of fluorescent polarizers.
U.S. published patent application 2004 0215015 A1 (published Oct. 28, 2004) and published PCT application WO 2004/096805 relate to certain water-soluble sulfoderivatives of perylenetetracarboxylic acid dibenzimidazole and the use of these materials to generate thin anisotropic films and optical elements based on the films. See also: T. Fiske, L. Ignatov, P. Lazarev, V. Nazarov, M. Paukshto Molecular Alignment in Crystal Polarizers and Retarders, Society for Information Display, Int. Symp. Digest of Technical Papers (Boston, Mass., May 19-24, 2002), p. 566 to 569. V. Nazarov, L. Ignatov, K. Kienskaya, Electronic Spectra of Aqueous Solutions and Films Made of Liquid Crystal Ink for Thin Film Polarizers, Mol. Mater. 14(2), 153 to 163 (2001). U.S. published application U.S. 2004 0058091 (published Mar. 25, 2004) relates to sulfoderivatives of 1,8-naphthoylene-1′,2′-benzimidazole and their use in the formation anisotropic thin films. In both published applications, the films are reported to be formed by application onto a substrate surface and oriented by any known method such as those described in PCT Publication Nos. WO 94/28073 and WO 00/25155.
U.S. published application 2003 0232153 A1 and published PCT application WO 2003/104242 relate to certain sulfoderivatives of indanthrone and their use to make anisotropic films.
Photoluminescent polarizers are an essential component of a recently developed polarization sensing technique for visual detection of analytes. In addition, photoluminescent polarizers can be used in place of the sheet polarizer and color filter combination that is employed in color liquid-crystal displays. Photoluminescent polarizers can be prepared by mechanically stretching polymers with incorporated fluorescent dyes. (Gryczynski, I.; Gryczynski, Z.; Lakowicz, J. R. Anal. Chem. (1999) 71, 1241-1251; Lakowicz, J. R.; Gryczynski, I.; Gryczynski, Z.; Dattelbaum, J. D. Anal. Biochem. (1999) 267, 397-405; Weder, C.; Sarwa, C.; Montali, A.; Bastiaansen, C.; Smith, P. Science (1998) 279, 835-837; Montali, A.; Bastiaansen, C.; Smith, P.; Weder, C. Nature (1998) 392, 261-264; Palmans, A. R. A.; Smith, P.; Weder, C. Macromolecules (1999), 32, 4677-4685.) This method, however, involves the laborious synthesis of fluorescent polymers or the impregnation of fluorescent dyes into stretchable polymers, the mechanical stretching of polymer films which limits the size of the photoluminescent polarizing films that can be produced by this method, and the additional step of mounting the polarizing film (the stretched polymer film) on the substrate of interest.
The present invention in one aspect provides materials, particularly fluorescent anisotropic materials, and methods for the preparation of anisotropic materials which can be employed as polarizers, particularly fluorescent polarizer and in other optical elements and devices/ Additionally the invention provides various compounds and compositions that are generally useful as dichroic dyes and fluorescent dyes in solution and in the solid phase.